CN108496272A - Include the non-aqueous electrolyte composition of fluorated solvent and 2- furanones - Google Patents

Abstract

It there is disclosed herein the non-aqueous electrolyte composition comprising fluorated solvent, carbonic ester cosolvent, at least one 2 furanone derivatives and at least one electrolytic salt.In some embodiments, these electrolyte compositions further include cyclic sulfates.The fluorated solvent can be fluorinated non-annularity carboxylate, fluorinated non-cyclic carbonate, fluorinated non-annularity ether, or combinations thereof.These electrolyte compositions are useful in electrochemical cell such as Li-ion batteries piles.

Description

Include the non-aqueous electrolyte composition of fluorated solvent and 2- furanones

Cross reference to related applications

This application claims the equity for the U.S. Provisional Application No. 62/246160 submitted on October 26th, 2015, this is faced When application be incorporated herein in its entirety by quoting mode.

Technical field

Disclosure content in this is related to gamma lactone and electricity comprising fluorated solvent, carbonic ester cosolvent, at least one conjugation Solve the electrolyte composition of matter salt.These electrolyte compositions are useful in electrochemical cell such as Li-ion batteries piles.

Background technology

Carbonate products are used for currently as electrolyte solvent containing by alkali metal, alkaline-earth metal or comprising these gold The non-aqueous batteries of electrode such as lithium ion battery made of the compound of category.Current lithium ion battery electrolyte solvent is typically Containing one or more linear carbonates, such as methyl ethyl carbonate, dimethyl carbonate or diethyl carbonate；And cyclic carbonate, such as Ethylene carbonate.However, under the greater than about cathode potential of 4.2V, these electrolyte solvent decomposable asymmetric choice nets, this can cause cell performance Loss of energy.

Various approach are had studied to overcome the limitation of usually used non-aqueous electrolytic solvent.For example, additive As cyclic carboxylic acids acid anhydride is applied in combination with certain electrolyte solvents (see, for example, the U.S. Patent Application Publication No. of Jeon et al. 2010/0273064 A1).In addition, have studied various fluorinated carboxylate electrolyte solvents for lithium ion battery (referring to Such as JP 4/328,915-B2, JP 3/444,607-B2 and the U.S. Patent number 8,097,368 of Nakamura et al.).Though These right electrolyte can be with high potential cathode such as 4V spinelles LiMn₂O₄It uses, but follows in the lithium ion battery of cathode Ring performance may be restricted, especially at high temperature.

There is still a need for when in lithium ion battery, particularly in high pressure (that is, up to about 5V) operation or combination high pressure the moon In use, the electrolyte composition with improved high temperature cyclic performance in such battery of pole.

Invention content

In one embodiment, a kind of electrolyte composition is there is provided herein, which includes：

A) fluorated solvent；

B) carbonic ester cosolvent；

C) at least one gamma lactone indicated by formula (II)

Wherein

R⁷、R⁸、R⁹And R¹⁰Be each independently H, F, linear chain or branched chain C₁To C₁₀The C of alkyl or linear chain or branched chain₁Extremely C₁₀Fluoroalkyl；And

D) at least one electrolytic salt.

In some embodiments, which includes 2 (5H)-furanones.

In one embodiment, which is：

A) the fluorinated non-annularity carboxylate being expressed from the next

R¹-COO-R²,

B) the fluorinated non-cyclic carbonate being expressed from the next

R³-OCOO-R⁴,

C) the fluorinated non-annularity ether being expressed from the next：

R⁵-O-R⁶,

Or mixtures thereof；

Wherein

i)R¹It is H, alkyl or fluoroalkyl；

ii)R³And R⁵It is fluoroalkyl each independently and can be same or different to each other；

iii)R²、R⁴And R⁶It is alkyl or fluoroalkyl each independently and can be same or different to each other；

iv)R¹And R²Any one of or both include fluorine；And

V) respectively as a pair of R¹And R²、R³And R⁴And R⁵And R⁶Including at least two carbon atoms but be no more than seven Carbon atom.

In some embodiments, which is fluorinated non-annularity carboxylate.In some embodiments, the fluorination is molten Agent is fluorinated non-cyclic carbonate.In some embodiments, which is fluorinated non-annularity ether.In some embodiments In, which includes at least one nonfluorinated carbonic ester.In some embodiments, which includes fluorine Change carbonic ester.In some embodiments, which includes ethylene carbonate.In some embodiments, the carbonic ester Cosolvent includes fluoroethylene carbonate.

In some embodiments, which further includes the cyclic sulfates indicated by formula (III)

Wherein each Q is independently hydrogen or optionally fluorinated vinyl, allyl, alkynyl, propargyl or C₁-C₃Alkane Base.In some embodiments, which includes ethyl sulfate.

In some embodiments, which further includes at least one component selected from the following terms：

I) borate indicated by formula (IV)：

LiBF_(4-2p)(C₂O₄)_p (IV)

Wherein p is 0,1 or 2；And/or

Ii) the oxalates indicated by formula (V)：

LiPF_(6-2q)(C₂O₄)_q (V)

Wherein q is 1,2 or 3.

In one embodiment, should include bis- (oxalic acid) lithium borates by the borate that formula (IV) indicates.In one embodiment In, should include three (oxalic acid) lithium phosphates by the oxalates that formula (V) indicates.

Another embodiment provides a kind of electrochemical cell, which includes：

(a) shell；

(b) it is disposed in the anode and cathode that in the shell and ionic conduction contacts each other；

(c) be disposed in the shell and provide the ionic conduction path between the anode and the cathode as draped over one's shoulders herein The electrolyte composition of dew；With

(d) porous septum between the anode and the cathode.

In another embodiment, which is Li-ion batteries piles.

It is described in detail

Described further below from reading, the feature and advantage of present disclosure will be easier to be managed by those of ordinary skill in the art Solution.It should be understood that present disclosure of the above and below described in the context of individual embodiment for clarity is certain Feature can also provide in single-element in combination.On the contrary, for brevity described in the context of single embodiment Present disclosure different characteristic can also by dividually or with any sub-portfolio provide.In addition, unless context is in addition clear It illustrates, can also include otherwise plural number (for example, " one/a kind of (a) " and " one/one kind (an) " can be with to referring to for odd number Refer to one/one kind or multiple/a variety of).

Unless expressly stated otherwise, the use of the numerical value in each range otherwise specified in this application is recited as closely Like value, as in illustrated range minimum value and maximum value all after word " about ".In this way, illustrated range it It is upper and under slight change can be used to implement the result essentially identical with the value within the scope of these.In addition, these ranges It discloses and is intended as the successive range including being worth each of between a minimum and a maximum value.

As above and through using present disclosure, unless otherwise specified, following term should be defined as follows：

Term " electrolyte composition " as used herein refers to the change for the electrolyte being adapted for use as in electrochemical cell Learn composition.

Term " electrolytic salt " as used herein refers to dissolving at least partly in the solvent of the electrolyte composition And ion is dissociated at least partly in the solvent of the electrolyte composition to form the ion of conducting electrolyte composition Salt.

Term " anode " as used herein refers to the electrode that electrochemical cell aoxidizes.In primary battery such as battery pack In, anode is electronegative electrode.In secondary (that is, chargeable) battery pack, anode is aoxidized in discharge process And the electrode restored in charging process.

Term " cathode " refers to the electrode that electrochemical cell restores.In primary battery such as battery pack, cathode is band The electrode of positive electricity.In secondary (that is, chargeable) battery pack, cathode is to occur to restore and charging in discharge process The electrode aoxidized in journey.

Term " Li-ion batteries piles " as used herein refers to that a type of rechargeable battery group, wherein lithium ion In discharge process cathode is moved to from anode and in charging process from movable cathode to anode.

Equilibrium potential between lithium and lithium ion is the potential of reference electrode, the reference electrode use with contain lithium salts The lithium metal of the non-aqueous electrolyte contact of (lithium salts is in the case where being enough to provide the concentration of lithium concentration of about 1 mol/L), and And it is subjected to sufficiently small electric current so that the potential of the reference electrode is not from its equilibrium valve (Li/Li⁺) significantly change.It is such Li/Li⁺The potential of reference electrode is designated herein as the value of 0.0V.The potential of anode or cathode refer to anode or cathode with Li/Li⁺Potential difference between reference electrode.Here, voltage refers to the voltage difference between the cathode and anode of battery, the battery Two electrodes cannot all be run under the potential of 0.0V.

Term " alkyl " as used herein refers to the chain hydrocarbon of the linear chain or branched chain containing the saturation from 1 to 10 carbon atom Base.The example of alkyl include methyl, ethyl, n-propyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, isopentyl, oneself Base, heptyl and octyl.

Term " fluoroalkyl " as used herein refers to the alkyl that wherein at least one hydrogen is replaced by fluorine.

Term " carbonic ester " as used herein refers to definitely organic carbonate, and the wherein organic carbonate is carbonic acid There is general formula R ' OCOOR ", wherein R ' and R " to be each independently selected from extremely for dialkyl diester derivative, the organic carbonate The alkyl of a few carbon atom, wherein alkyl substituent are identical or different, saturated or unsaturated, substitutions or unsubstituted , cyclic structure can be formed via the atom of interconnection, and/or including cyclic structure as any one of these alkyl or two The substituent group of person.

Electrolyte composition is there is disclosed herein, these electrolyte compositions include the following terms or consisting essentially of： A) fluorated solvent；B) carbonic ester cosolvent；C) at least one gamma lactone as in this disclosure；And d) at least one electrolyte Salt.The fluorated solvent can be fluorinated non-annularity carboxylate, fluorinated non-cyclic carbonate, fluorinated non-annularity ether or its Combination.In one embodiment, which is fluorinated non-annularity carboxylate.In one embodiment, the fluorated solvent It is fluorinated non-cyclic carbonate.In an a little embodiments, which is fluorinated non-annularity ether.As used herein , term " fluorated solvent " and " carbonic ester cosolvent " they refer to the different of the electrolyte composition, i.e., different chemicalization Close object.

In one embodiment, these electrolyte compositions further include cyclic sulfates.

These electrolyte compositions are useful in electrochemical cell, particularly Li-ion batteries piles.It has been found that packet Containing the fluorated solvent, the carbonic ester cosolvent, at least one gamma lactone as in this disclosure and at least one electrolytic salt or base The electrolyte composition being made from it in sheet can provide the secondary electricity with high-energy density and improved high temperature cyclic performance Pond.

Phrase " substantially by ... form ", which refers to the electrolyte composition, can contain as group a) and b) listed It is allocated as solvent.The electrolyte composition free or substantially free of do not list as a) or b) one of component other are molten Agent.Substantially free refer to a kind of specific component be less than 5% by weight with the total weight based on the electrolyte composition, Or it is less than 3% by weight or is less than 1% by weight or is less than 0.5% by weight and exist.In addition, language " substantially By ... form " refer to the electrolyte composition free or substantially free of other electrolytic salts for not being lithium salts.

Suitable fluorinated non-annularity carboxylate is expressed from the next

R¹-COO-R²

Wherein

i)R¹It is H, alkyl or fluoroalkyl；

ii)R²It is alkyl or fluoroalkyl；

iii)R¹And R²Any one of or both include fluorine；And

Iv) as a pair of R¹And R²Including at least two carbon atoms but be no more than seven carbon atoms.

In one embodiment, R¹It is H and R²It is fluoroalkyl.In one embodiment, R¹It is alkyl and R²It is fluothane Base.In one embodiment, R¹It is fluoroalkyl and R²It is alkyl.In one embodiment, R¹It is fluoroalkyl and R²It is fluothane Base, and R¹And R²It can be same or different to each other.In one embodiment, R¹Including a carbon atom.Implement at one In example, R¹Including two carbon atoms.

In another embodiment, R¹And R²It is as defined above herein, and as a pair of R¹And R²Including extremely Lack two carbon atoms but be no more than seven carbon atoms and further include at least two fluorine atoms, condition is R¹And R²Not Contain FCH₂Group or-FCH- groups.

The example of suitable fluorinated non-annularity carboxylate includes but not limited to CH₃-COO-CH₂CF₂H (2,2- bis-fluoro ethyls Acetic acid esters, CAS 1550-44-3), CH₃-COO-CH₂CF₃(2,2,2- trifluoroethyl acetic acid esters, CAS 406-95-1), CH₃CH₂-COO-CH₂CF₂H (2,2- bis-fluoro ethyls propionic esters, CAS 1133129-90-4), CH₃-COO-CH₂CH₂CF₂H(3,3- Difluoro propyl-acetic acid ester), CH₃CH₂-COO-CH₂CH₂CF₂H (bis- fluoropropyl propionic esters of 3,3-), HCF₂-CH₂-CH₂-COO- CH₂CH₃(ethyl 4,4- difluoro butyrates, CAS 1240725-43-2), H-COO-CH₂CF₂H (bis-fluoro ethyls formic acid esters, CAS Number 1137875-58-1), H-COO-CH₂CF₃(trifluoroethyl formic acid esters, CAS 32042-38-9), F₂CHCH₂-COO-CH₃(first Base 3,3- difluoros propionic ester), F₂CHCH₂-COO-CH₂CH₃(ethyl 3,3- difluoros propionic ester) and its mixture.In a reality It applies in example, which includes 2,2- bis-fluoro ethyls acetic acid esters (CH₃-COO-CH₂CF₂H).Implement at one In example, which includes 2,2- bis-fluoro ethyls propionic esters (CH₃CH₂-COO-CH₂CF₂H).Implement at one In example, which includes 2,2,2- trifluoroethyl acetic acid esters (CH₃-COO-CH₂CF₃).In one embodiment In, which includes 2,2- bis-fluoro ethyls formic acid esters (H-COO-CH₂CF₂H)。

Suitable fluorinated non-cyclic carbonate is expressed from the next

R³-OCOO-R⁴

Wherein

i)R³It is fluoroalkyl；

ii)R⁴It is alkyl or fluoroalkyl；And

Iii) as a pair of R³And R⁴Including at least two carbon atoms but be no more than seven carbon atoms.

In one embodiment, R³It is fluoroalkyl and R⁴It is alkyl.In one embodiment, R³It is fluoroalkyl and R⁴ It is fluoroalkyl, and R³And R⁴It can be same or different to each other.In one embodiment, R³Including a carbon atom.One In a embodiment, R³Including two carbon atoms.

In another embodiment, R³And R⁴It is as defined above herein, and as a pair of R³And R⁴Including extremely Lack two carbon atoms but be no more than seven carbon atoms and further include at least two fluorine atoms, condition is R³And R⁴Not Contain FCH₂Group or-FCH- groups.

The example of suitable fluorinated non-cyclic carbonate includes but not limited to CH₃-OC(O)O-CH₂CF₂H (methyl 2,2- Bis-fluoro ethyls carbonic ester, CAS 916678-13-2), CH₃-OC(O)O-CH₂CF₃(methyl 2,2,2- trifluoroethyl carbonic esters, CAS 156783-95-8), CH₃-OC(O)O-CH₂CF₂CF₂H (2,2,3,3- tetrafluoro propyl carbonate of methyl, No. CAS 156783-98-1)、HCF₂CH₂-OCOO-CH₂CH₃(2,2- bis-fluoro ethyls ethyl carbonate esters, CAS 916678-14-3) and CF₃CH₂-OCOO-CH₂CH₃Or mixtures thereof (2,2,2- trifluoroethyl ethyl carbonate esters, CAS 156783-96-9),.

Suitable fluorinated non-annularity ether is expressed from the next

R⁵-O-R⁶

Wherein

i)R⁵It is fluoroalkyl；

ii)R⁶It is alkyl or fluoroalkyl；And

Iii) as a pair of R⁵And R⁶Including at least two carbon atoms but be no more than seven carbon atoms.

In one embodiment, R⁵It is fluoroalkyl and R⁶It is alkyl.In one embodiment, R⁵It is fluoroalkyl and R⁶ It is fluoroalkyl, and R⁵And R⁶It can be same or different to each other.In one embodiment, R⁵Including a carbon atom.One In a embodiment, R⁵Including two carbon atoms.

In another embodiment, R⁵And R⁶It is as defined above herein, and as a pair of R⁵And R⁶Including extremely Lack two carbon atoms but be no more than seven carbon atoms and further include at least two fluorine atoms, condition is R⁵And R⁶Not Contain FCH₂Group or-FCH- groups.

The example of suitable fluorinated non-annularity ether includes but not limited to HCF₂CF₂CH₂-O-CF₂CF₂H (CAS 16627- 68-2) and HCF₂CH₂-O-CF₂CF₂H (CAS 50807-77-7).

The fluorated solvent may include fluorinated non-annularity carboxylate, fluorinated non-cyclic carbonate, fluorinated non-annularity Or mixtures thereof ether,.As used herein, term " its mixture " includes mixture in solvent classification and in solvent Both mixture between not, for example, two or more fluorinated non-annularity carboxylates mixture, and also have such as fluorine The mixture of the non-annularity carboxylate and fluorinated non-cyclic carbonate of change.Non-limiting examples include 2,2- bis-fluoro ethyls acetic acid The mixture of ester and 2,2- bis-fluoro ethyls propionic esters；And 2,2- bis-fluoro ethyls acetic acid esters and 2,2- bis-fluoro ethyls methyl carbonics Mixture.In one embodiment, which includes 2,2- bis-fluoro ethyls acetic acid esters；2,2- bis-fluoro ethyls methyl carbonic acids Ester；Or mixtures thereof.

In one embodiment, which is：

A) the fluorinated non-annularity carboxylate being expressed from the next：

R¹-COO-R²,

B) the fluorinated non-cyclic carbonate being expressed from the next：

R³-OCOO-R⁴,

C) the fluorinated non-annularity ether being expressed from the next：

R⁵-O-R⁶,

Or mixtures thereof；

Wherein

i)R¹It is H, alkyl or fluoroalkyl；

ii)R³And R⁵It is fluoroalkyl each independently and can be same or different to each other；

iii)R²、R⁴And R⁶It is alkyl or fluoroalkyl each independently and can be same or different to each other；

iv)R¹And R²Any one of or both include fluorine；And

V) respectively as a pair of R¹And R²、R³And R⁴And R⁵And R⁶Including at least two carbon atoms, but it is no more than seven Carbon atom.

In another embodiment, which is

A) the fluorinated non-annularity carboxylate being expressed from the next：

R¹-COO-R²,

B) the fluorinated non-cyclic carbonate being expressed from the next：

R³-OCOO-R⁴,

C) the fluorinated non-annularity ether being expressed from the next：

R⁵-O-R⁶,

Or mixtures thereof；

Wherein

i)R¹It is H, alkyl or fluoroalkyl；

ii)R³And R⁵It is fluoroalkyl each independently and can be same or different to each other；

iii)R²、R⁴And R⁶It is alkyl or fluoroalkyl each independently and can be same or different to each other；

iv)R¹And R²Any one of or both include fluorine；And

V) respectively as a pair of R¹And R²、R³And R⁴And R⁵And R⁶Including at least two carbon atoms but be no more than seven Carbon atom and at least two fluorine atoms are further included, condition is R¹、R²、R³、R⁴、R⁵And R⁶FCH is not all contained₂Group Or-FCH- groups.

In the electrolyte composition disclosed here, the desirable characteristic of the electrolyte composition, the fluorination are depended on Or mixtures thereof solvent can be used with various amounts.In one embodiment, which includes the electrolyte composition By weight about 5% to about 95%.In another embodiment, the fluorated solvent include the electrolyte composition by weight Meter about 10% to about 90%.In another embodiment, the fluorated solvent include the electrolyte composition by weight about 10% to about 80%.In another embodiment, the fluorated solvent include the electrolyte composition by weight about 30% to About 70%.In another embodiment, which includes by weight about the 50% to about 70% of the electrolyte composition. In another embodiment, which includes by weight about the 60% to about 80% of the electrolyte composition.Another In a embodiment, which includes by weight about the 45% to about 65% of the electrolyte composition.In another implementation In example, which includes by weight about the 5% to about 30% of the electrolyte composition.In another embodiment, should Fluorated solvent includes by weight about the 60% to about 65% of the electrolyte composition.In another embodiment, the fluorination is molten Agent includes by weight about the 20% to about 45% of the electrolyte composition.

It is suitable for fluorinated non-annularity carboxylate as used herein, fluorinated non-cyclic carbonate and fluorinated acyclic Shape ether can be prepared using known method.For example, can make chloroacetic chloride and 2,2- difluoroethanols (are with or without base catalysis Agent) it reacts to form 2,2- bis-fluoro ethyls acetic acid esters.Additionally, 2,2- bis-fluoro ethyls acetic acid esters and 2,2- bis-fluoro ethyls propionic esters The method (WO2009/040367A1, example 5) described by Wiesenhofer et al. can be used to be prepared.Alternatively, 2,2- bis-fluoro ethyls acetic acid esters can use the method described in this following Examples to be prepared.Other fluorinated non-annularity carboxylics Acid esters can be prepared using identical method using different starting carboxylic acids' salt.Similarly, can make methylchloroformate with 2,2- difluoroethanols are reacted to form methyl 2,2- bis-fluoro ethyls carbonic esters.HCF₂CF₂CH₂-O-CF₂CF₂The synthesis of H can pass through 2,2,3,3- tetrafluoropropanols are made to be reacted in the presence of alkali (for example, NaH etc.) to carry out with tetrafluoroethene.Similarly, 2,2- difluoros Ethyl alcohol produces HCF with reacting for tetrafluoroethene₂CH₂-O-CF₂CF₂H.Alternatively, one in fluorated solvent disclosed here It can for example be obtained a bit from the company trade of such as Matrix Scientific (Columbia SC).In order to best as a result, It is desirable that purifying these fluorinated non-annularity carboxylates and fluorinated non-cyclic carbonate at least about 99.9%, Geng Te Not at least about 99.99% purity level.Fluorated solvent disclosed here can use distillating method as being evaporated in vacuo or revolving Spinning band distillation purifies.

Electrolyte composition disclosed here includes at least one carbonic ester cosolvent.The carbonic ester cosolvent may include Cyclic annular or non-cyclic carbonate or cyclic carbonate and non-cyclic carbonate mixture.The carbonic ester cosolvent may include The mixture of fluorocarbons acid esters, nonfluorinated carbonic ester or fluorocarbons acid esters and nonfluorinated carbonic ester.In one embodiment, the carbon Acid esters cosolvent includes cyclic carbonate.In one embodiment, which includes non-cyclic carbonate.At one In embodiment, which includes nonfluorinated carbonic ester.In one embodiment, which includes fluorination Carbonic ester.It is desirable that using being battery pack grade or the purity at least about 99.9%, for example, at least about 99.99% Horizontal carbonic ester.Nonfluorinated carbonic ester and fluorocarbons acid esters are both commercially available, or can be by known in the art Method prepare.

Suitable nonfluorinated carbonic ester includes ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbon Sour Asia propyl ester, vinylene carbonate, dimethyl dicarbonate butyl ester, dipropyl carbonate, methyl propyl carbonate, carbonic acid ethyl propyl Asia ethylene Ester, carbonic acid first butyl ester, ethyl butyl carbonate, the third butyl ester of carbonic acid, dibutyl carbonate, vinyl ethylene carbonate, carbonic acid dimethyl are sub- Or mixtures thereof vinyl acetate.In some embodiments, which includes ethylene carbonate, propylene carbonate, carbonic acid Methyl ethyl ester, dimethyl carbonate, diethyl carbonate, vinylene carbonate, or mixtures thereof.In one embodiment, the nonfluorinated Carbonic ester includes ethylene carbonate.In one embodiment, which includes propylene carbonate.In one embodiment In, which includes dimethyl carbonate.In one embodiment, which includes methyl ethyl carbonate. In one embodiment, which includes diethyl carbonate.In one embodiment, which includes Vinylene carbonate.

Suitable fluorocarbons acid esters includes that 4- fluorine ethylenecarbonate (is abbreviated as FEC, it is fluoro- to be also known as 4- herein herein The amyl- 2- ketone of 1,3- dioxy rings), two fluoro ethyl isomers of carbonic acid, three fluoro ethyl isomers of carbonic acid, carbonic acid four fluoro it is sub- Ethyl ester, 2,2,3,3- tetrafluoro hydroxypropyl methyls carbonic ester, bis- (tetra- fluoropropyls of 2,2,3,3-) carbonic esters, bis- (2,2,2- trifluoroethyls) Carbonic ester, 2,2,2- trifluoroethyls methyl carbonic, bis- (2,2- bis-fluoro ethyls) carbonic esters, 2,2- bis-fluoro ethyls methyl carbonic acids Or mixtures thereof ester or methyl 2,3,3- trifluoros allyl carbonate,.In one embodiment, which includes carbon Sour fluoro ethyl.In one embodiment, which includes the amyl- 2- ketone of fluoro- 1, the 3- dioxies rings of 4-；4,5- bis- is fluoro- The amyl- 2- ketone of 1,3- dioxy rings；The bis- amyl- 2- ketone of fluoro- 4- methyl-1,3-dioxies ring of 4,5-；Bis- fluoro- 4,5- dimethyl -1,3- of 4,5- The amyl- 2- ketone of dioxy ring；The bis- amyl- 2- ketone of fluoro- 1,3- dioxies ring of 4,4-；The tri- amyl- 2- ketone of fluoro- 1,3- dioxies ring of 4,4,5-；Or it is mixed Close object.Fluorination cyclic carbonate disclosed here can be obtained commercially or be prepared using methods known in the art.

In another embodiment, suitably fluorination cyclic carbonate can be indicated by formula (I)

Wherein

I) A, B, C and D are respectively H, F, saturated or unsaturated C₁To C₄Alkyl or saturated or unsaturated C₁To C₄Fluorine Alkyl, and can be the same or different from each other；And

Ii) at least one of A, B, C and D include fluorine.

As used herein, term " undersaturated " refers to the olefinic formula unsaturated group containing at least one carbon-to-carbon double bond Group.

In the electrolyte composition disclosed here, the desirable characteristic of the electrolyte composition, the carbonic acid are depended on Ester cosolvent can be used with various amounts.In one embodiment, the total weight based on the electrolyte composition, the electrolyte Composition includes one or more carbonic esters from about 0.5 weight percent to about 99 weight percent.In other embodiment In, which can include from about 0.5 weight percent to about 95 weight percent or from about 0.5 weight percent Than to about 90 weight percent or from about 0.5 weight percent to about 85 weight percent or from about 0.5 to about 80 weight hundred Point ratio or from about 0.5 to about 75 weight percent or from about 0.5 weight percent to about 70 weight percent or from about 0.5 Weight percent is to about 65 weight percent or from about 0.5 weight percent to about 60 weight percent or from about 0.5 weight Percentage is to about 55 weight percent or from about 0.5 weight percent to about 50 weight percent or from about 0.5 weight percent Than to about 45 weight percent or from about 0.5 weight percent to about 40 weight percent or from about 0.5 weight percent to About 35 weight percent or from about 0.5 weight percent to about 30 weight percent or from about 0.5 weight percent to about 25 Weight percent or from about 0.5 weight percent to about 20 weight percent or from about 0.5 weight percent to about 15 weight Percentage or from about 0.5 weight percent to about 10 weight percent or from about 0.5 weight percent to about 5 weight percents Than or from about 0.5 weight percent to about 3 weight percent the carbonic ester cosolvent.

In some embodiments, the electrolyte composition include from about 5 weight percent to the 2 of about 95 weight percent, 2- bis-fluoro ethyls acetic acid esters.In some embodiments, which includes from about 10 weight percent to about 90 weight Percentage or from about 20 weight percent to about 80 weight percent or from about 30 weight percent to about 80 weight percent, Or from about 40 weight percent to about 80 weight percent or from about 50 weight percent to about 80 weight percent or from about The 2,2- bis-fluoro ethyls acetic acid esters of 60 weight percent to about 80 weight percent.In some embodiments, 2, the 2- difluoro second Yl acetate is present in the weight percent limited by lower and upper limit in the electrolyte composition.The lower limit of the range is 5, 10,20,25,30,35,40,45,50,55,60 or 65, and the upper limit of the range is 70,75,80,85,90,95,96,97, 98 or 99.All weight percent are based on the total weight of the electrolyte composition.

Electrolyte composition disclosed here includes the gamma lactone of at least one conjugation.Suitable gamma lactone includes by formula Those of (II) indicate：

Wherein R⁷、R⁸、R⁹And R¹⁰Be each independently H, F, linear chain or branched chain C₁To C₁₀Alkyl or linear chain or branched chain C₁To C₁₀Fluoroalkyl.In formula (II), R⁷、R⁸、R⁹And R¹⁰Can be identical or different.The example of suitable alkyl includes first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, hexyl and heptyl.Suitable fluothane The example of base includes wherein at least one hydrogen by fluorine-substituted methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl Base, sec-butyl, tertiary butyl, amyl, hexyl and heptyl and perfluorinated alkyl (including-CF₃、-CF₂CF₃、-CF₂CF₂CF₃, with And-CF (CF₃)₂).The example of suitable gamma lactone includes 2 (5H)-furanones and 3- methyl -2 (5H)-furanone.In a reality It applies in example, which includes 2 (5H)-furanones.2 (5H)-furanones are by formula (II) expression, wherein R⁷、R⁸、R⁹And R¹⁰ Individually H.In one embodiment, which includes 3- methyl -2 (5H)-furanone, wherein in formula (II), R⁷It is first Base and R⁸、R⁹And R¹⁰Individually H.

Gamma lactone as in this disclosure can be obtained commercially or be prepared using methods known in the art.It enables The gamma lactone is desirably purified at least about 99.0%, for example, at least about 99.9% purity level by people.Purifying can make It is carried out with methods known in the art.

In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight Percentage to about 5 weight percent gamma lactone.In some embodiments, weight of the gamma lactone to be limited by lower and upper limit Amount percentage is present in the electrolyte composition.The lower limit of the range is 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8, 0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4 or 2.5, and should The upper limit of range is 2.6,2.7,2.8,2.9,3.0,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4.0,4.1, 4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 or 5.0.All weight percent are based on the electrolyte composition Total weight.

In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, ethylene carbonate and 2 (5H)-furanone.In some embodiments, the electrolyte composition include 2,2- bis-fluoro ethyls acetic acid esters, dimethyl carbonate, with And 2 (5H)-furanone.In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, polypropylene carbonate Ester and 2 (5H)-furanones.In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, carbonic acid Methyl ethyl ester and 2 (5H)-furanones.In some embodiments, the electrolyte composition include 2,2- bis-fluoro ethyls acetic acid esters, Fluoroethylene carbonate and 2 (5H)-furanones.In some embodiments, which includes 2,2- bis-fluoro ethyls Acetic acid esters；2,2- bis-fluoro ethyls methyl carbonics；Or mixtures thereof, carbonic ester cosolvent and 2 (5H)-furanones.

Optionally, electrolyte composition disclosed here can further include the cyclic sulfates indicated by formula (III)：

Wherein each Q is independently hydrogen or optionally fluorinated vinyl, allyl, alkynyl, propargyl or C₁-C₃Alkane Base.Vinyl (H₂C=CH-), allyl (H₂C=CH-CH₂), alkynyl (HC ≡ C-), propargyl (HC ≡ C-CH₂) or C₁- C₃Alkyl can be individually unsubstituted or partially or fully fluorinated.Two or more cyclic sulfates can also be used Mixture.Suitable cyclic sulfates include ethyl sulfate (penta ring of 1,3,2- dioxies thia, 2,2- dioxide)；1,3, Penta ring 4- acetenyls of 2- dioxies thia-, 2,2- dioxide；Penta ring of 1,3,2- dioxies thia, 4- vinyl-, 2,2- titanium dioxides Object；Penta ring of 1,3,2- dioxies thia, divinyl-, 2,2- dioxide；Penta ring of 1,3,2- dioxies thia, 4- methyl-, 2,2- Dioxide；And penta ring of 1,3,2- dioxies thia, 4,5- dimethyl-, 2,2- dioxide.In one embodiment, the ring Shape sulfuric ester includes ethyl sulfate.

In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight Percentage to about 5 weight percent the optional cyclic sulfates.In some embodiments, the cyclic sulfates are with by lower limit The weight percent limited with the upper limit is present in the electrolyte composition.The lower limit of the range is 0.1,0.2,0.3,0.4, 0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、 2.4 or 2.5, and the upper limit of the range is 2.6,2.7,2.8,2.9,3.0,3.1,3.2,3.3,3.4,3.5,3.6,3.7, 3.8,3.9,4.0,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 or 5.0.All weight percent are based on The total weight of the electrolyte composition.

In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight Percentage is to the gamma lactone of about 5 weight percent and the cyclic annular sulfuric acid of about 0.1 weight percent to about 5 weight percent Ester.In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight percent Than the cyclic sulfates of gamma lactone and about 0.1 weight percent to about 5 weight percent to about 2.5 weight percent. In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight percent extremely The cyclic sulfates of the gamma lactone of about 5 weight percent and about 0.1 weight percent to about 2.5 weight percent.

In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight Percentage is to the gamma lactone of about 5 weight percent and the sulfuric acid Asia second of about 0.1 weight percent to about 5 weight percent Ester.In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight percent Than the ethyl sulfate of gamma lactone and about 0.1 weight percent to about 5 weight percent to about 2.5 weight percent. In some embodiments, the total weight based on the electrolyte composition, the electrolyte composition include about 0.1 weight percent extremely The ethyl sulfate of the gamma lactone of about 5 weight percent and about 0.1 weight percent to about 2.5 weight percent.

Optionally, electrolyte composition disclosed here further includes at least one component selected from the following terms：

I) borate indicated by formula (IV)：

LiBF_(4-2p)(C₂O₄)_p (IV)

Wherein p is 0,1 or 2；And/or

Ii) the oxalates indicated by formula (V)：

LiPF_(6-2q)(C₂O₄)_q (V)

Wherein q is 1,2 or 3.

In one embodiment, which includes the borate with formula (IV).In one embodiment, which includes Oxalates with formula (V).In one embodiment, which includes borate with formula (IV) and with formula (V) Oxalates.

Borate disclosed here can be LiBF4 (LiBF₄), difluoro (oxalic acid) lithium borate [LiBF₂(C₂O₄)]、 Bis- (oxalic acid) lithium borate [LiB (C₂O₄)₂Or mixtures thereof].In one embodiment, which includes LiBF4. In one embodiment, which includes difluoro (oxalic acid) lithium borate.In one embodiment, which includes bis- (oxalic acid) Lithium borate.The mixture of two or more in these can also be used.Borate disclosed here can be commercial obtains It is obtaining or using methods known in the art preparation.

In one embodiment, which includes about 0.001 weight percent to about 15 weight percent Borate with formula (IV).In other embodiments, which can include about 0.01 weight percent to about 15 weight percent or about 0.1 weight percent to about 15 weight percent or about 1 weight percent to about 15 weight percents Than or about 1 weight percent to about 10 weight percent or about 1 weight percent to about 5 weight percent or about 0.5 weight Percentage to about 3 weight percent the borate.

Oxalates disclosed here can be tetrafluoro (oxalic acid) lithium phosphate [LiPF₄(C₂O₄)], bis- (oxalic acid) lithium phosphates of difluoro [LiPF₂(C₂O₄)₂], three (oxalic acid) lithium phosphate [LiP (C₂O₄)₃Or mixtures thereof],.In one embodiment, the oxalates packet Include tetrafluoro (oxalic acid) lithium phosphate.In one embodiment, which includes bis- (oxalic acid) lithium phosphates of difluoro.In one embodiment In, which includes three (oxalic acid) lithium phosphates.The mixture of two or more in these can also be used.It is disclosed herein Oxalates can be obtained commercially or be prepared using methods known in the art.

In one embodiment, which includes about 0.001 weight percent to about 15 weight percent Oxalates with formula (V).In other embodiments, which can include about 0.01 weight percent to about 15 Weight percent or about 0.1 weight percent to about 15 weight percent or about 1 weight percent to about 15 weight percent, Or about 1 weight percent to about 10 weight percent or about 1 weight percent to about 5 weight percent or about 0.5 weight hundred Divide than the oxalates to about 3 weight percent.

In one embodiment, the total weight based on the electrolyte composition, the electrolyte composition include about 0.001 weight Measure percentage to the borate of about 15 weight percent, the oxalates, or combinations thereof.In one embodiment, the electrolyte Composition include bis- (oxalic acid) lithium borates of about 0.1 weight percent to about 5 weight percent, three (oxalic acid) lithium phosphates or its Mixture.

In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, ethylene carbonate and 2 (5H)-furanone.In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, ethylene carbonate, 2 (5H)-furanone and LiBOB.In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid esters, carbon Dimethyl phthalate and 2 (5H)-furanones.In some embodiments, which includes 2,2- bis-fluoro ethyls acetic acid Ester, dimethyl carbonate, 2 (5H)-furanones and LiBOB.In some embodiments, which includes 2,2- bis- Fluoro ethyl acetic acid esters, propylene carbonate and 2 (5H)-furanones.In some embodiments, which includes 2, 2- bis-fluoro ethyls acetic acid esters, propylene carbonate, 2 (5H)-furanones and LiBOB.In some embodiments, the electrolyte group It includes 2,2- bis-fluoro ethyls acetic acid esters, methyl ethyl carbonate and 2 (5H)-furanones to close object.In some embodiments, the electrolysis Matter composition includes 2,2- bis-fluoro ethyls acetic acid esters, methyl ethyl carbonate, 2 (5H)-furanones and LiBOB.

Electrolyte composition disclosed here also contains at least one electrolytic salt.Suitable electrolytic salt includes but unlimited In

Lithium hexafluoro phosphate (LiPF₆)、

Three (pentafluoroethyl group) three lithium fluophosphate (LiPF₃(C₂F₅)₃)、

Bis- (trifluoromethane sulfonyl group) imide lis,

Bis- (hexafluoroethane sulfonyl) imide lis,

(fluorosulfonyl) (nine fluorine butane sulfonyls) imide li,

Bis- (fluorosulfonyl) imide lis,

LiBF4,

Lithium perchlorate,

Hexafluoroarsenate lithium,

Trifluoromethayl sulfonic acid lithium,

Three (trifluoromethane sulfonyl groups) methylate lithium,

Bis- (oxalic acid) lithium borates,

Difluoro (oxalic acid) lithium borate,

Li₂B₁₂F_12-xH_x(wherein x be equal to 0 to 8) and

Lithium fluoride and anion receptor such as B (OC₆F₅)₃Mixture.

The mixture of two or more in these or comparable electrolytic salt can also be used.In one embodiment In, which includes lithium hexafluoro phosphate.The electrolytic salt can be with from about 0.2M to about 2.0M, for example from about 0.3M to About 1.5M is for example present in from about 0.5M to the amount of about 1.2M in the electrolyte composition.

Electrolyte composition disclosed here can additionally or optionally include that those of ordinary skill in the art are known normal Additive that is useful in rule electrolyte composition, being particularly used in Li-ion batteries piles.For example, electrolyte disclosed here Composition can also include that gas reduces additive, these additives are for reducing the charging and discharging in Li-ion batteries piles The amount of the gas generated in journey is useful.It can be used with any effective quantity, but can be wrapped that gas, which reduces additive, Include with comprising the electrolyte composition from about 0.05wt% to about 10wt%, alternatively from about 0.05wt% to about 5wt%, Or alternatively the electrolyte composition from about 0.5wt% to about 2wt%.

Conventionally known suitable gas reduces additive, such as：Halobenzene, such as fluorobenzene, chlorobenzene, bromobenzene, iodobenzene or halogen Alkylbenzene；1,3- propane sultones；Succinic anhydride；Acetenyl sulfonyl benzene；2- sulfobenzoic acid cyclic anhydrides；Divinylsulfone；Three Phenyl phosphate ester (TPP)；Diphenyl phosphate mono-n-butylester (DMP)；Gamma-butyrolacton；2,3 dichlro 1,4 naphtho quinone；1,2- naphthoquinones；2, Bis- bromo- 1,4- naphthoquinones of 3-；The bromo- 1,2- naphthoquinones of 3-；2- acetyl furans；2- acetyl group -5- methylfurans；2-methylimidazole 1- (phenyl sulfonyl) pyrroles；2,3- benzofurans；Fluoro- ring triphosphine nitrile, such as 2,4,6- tri- fluoro- 2- phenoxy groups -4,6- dipropoxies - Tri- fluoro- 2- of ring triphosphine nitrile and 2,4,6- (3- (trifluoromethyl) phenoxy group) -6- ethyoxyls-ring triphosphine nitrile；Benzotriazole；Perfluor second Olefinic carbon acid esters；Methyl phenyl ethers anisole；Diethyl phosphonate；The substituted dioxolanes of fluoroalkyl-, such as 2- trifluoromethyls dioxolanes and 2,2- Bis trifluoromethyl -1,3- dioxolanes；Three methylene ester of boric acid；- 2 (3H)-furanone of dihydro-3-hydroxy -4,5,5- trimethyls；Two - 3 (2H)-furanone of hydrogen -2- methoxyl group -5,5- dimethyl；Dihydro -5,5- dimethyl -2,3- furasndiones；Propene sultone； Diglycolic acid acid anhydrides；Two -2-propynyl oxalates；4- hydroxyl -3- pentenoic acid y-lactones；CF₃COOCH₂C(CH₃) (CH₂OCOCF₃)₂；CF₃COOCH₂CF₂CF₂CF₂CF₂CH₂OCOCF₃；Alpha-methylene-gamma-butyrolactone；3- methyl -2 (5H)-furans Ketone；5,6- dihydro -2- pyranone；Diethylene glycol diacetate；Triethylene glycol dimethacrylate；Triethylene-glycol diacetate；1,2- Ethane disulfonic acid acid anhydride；1,3- propanedisulfonic acid acid anhydrides；Two thiophene ring in heptan of 2,2,7,7- tetroxide 1,2,7- oxa-s；Methyl -2,2 3-, 5,5- tetroxide 1,2,5- oxa- dithiolanes；Three phosphonitrile of hexakis-methoxy basic ring；Two fluoro- 1,3- dioxies of 4,5- dimethyl -4,5- The amyl- 2- ketone of ring；Five three azepines of fluoro- 2,2,4,4,6,6- hexahydros -1,3,5,2,4,6- of 2- ethyoxyls -2,4,4,6,6-, three phospha Benzene；Five three azepines of fluoro- 2,2,4,4,6,6- hexahydros -6- methoxyl groups -1,3,5,2,4,6- of 2,2,4,4,6-, three phospha benzene；4,5- bis- The fluoro- amyl- 2- ketone of 1,3- dioxies ring；Bis- (ethylidine the sulfonyl)-butane of 1,4-；Bis- (vinylsulfonyl)-methane；1,3- is bis- (ethylidine sulfonyl)-propane；Bis- (ethylidine the sulfonyl)-ethane of 1,2-；Ethylene carbonate；Diethyl carbonate；Carbonic acid diformazan Ester；Methyl ethyl carbonate；And 1,1'- [oxygroup is bis- (methylene sulfonyl)] double-ethylene.

Other the suitable additives that can be used are HF scavengers, such as silane, silazane (Si-NH-Si), epoxidation Salt (such as lithium oxalate), the B of object, amine, aziridine (containing there are two carbon), carbonic acid₂O₅And ZnO.

Another embodiment provides a kind of methods being used to form the electrolyte composition.This method includes：

Combination：

A) fluorated solvent；

B) carbonic ester cosolvent；

C) at least one gamma lactone indicated by formula (II)

Wherein

R⁷、R⁸、R⁹And R¹⁰Be each independently H, F, linear chain or branched chain C₁To C₁₀The C of alkyl or linear chain or branched chain₁Extremely C₁₀Fluoroalkyl；And

D) at least one electrolytic salt, to form electrolyte composition.These components can be in any suitable order Combination.The combination step can be completed by adding each component of the electrolyte composition in order or simultaneously.In some realities It applies in example, by component a), b) and c) combination to be to be made the first solution.After forming first solution, by a certain amount of electricity Solution matter salt is added in first solution, to generate the electrolyte composition of the lithium salts with desired concentration.In some implementations In example, by component a) and b) combination is to be made initial soln.After forming the initial soln, by a certain amount of electrolytic salt It is added in the initial soln, to generate the electrolyte composition of the lithium salts with about desired concentration, and then addition group Divide c) to generate the electrolyte composition of lithium salts and component c) with desired concentration.Typically, in the addition of these components During and/or after stir the electrolyte composition, to form uniform mixture.The fluorated solvent is as being disclosed herein 's.

In another embodiment, there is provided herein a kind of electrochemical cell, the electrochemical cell include the following terms or It is consisting essentially of：

(a) shell；

(b) it is disposed in the anode and cathode that in the shell and ionic conduction contacts each other；

(c) be disposed in the shell and provide the ionic conduction path between the anode and the cathode as existed above The electrolyte composition of this description；With

(d) porous septum between the anode and the cathode.

In some embodiments, which is Li-ion batteries piles.

The shell can be any suitable container for accommodating electrochemical cell components.Case material is known in the art , and may include such as metal and polymer-type shell.It is suitable although the shape of the shell is not especially important Shell can be made with the shape of small or big cylinder, prismatic case or bag.

Depending on the type of electrochemical cell, the anode and the cathode can be made of any suitable conductive material.Sun The suitable example of pole material includes but not limited to lithium metal, lithium metal alloy, lithium titanate, aluminium, platinum, palladium, graphite, oxo transition metal The tin oxide of compound and lithiumation.The suitable example of cathode material includes but not limited to graphite, aluminium, platinum, palladium, includes lithium or sodium Electroactive transition metal oxide, indium tin oxide and conducting polymer such as polypyrrole and polyethylene ferrocene.

In some embodiments, suitable cathode material may include such as cathode active material comprising lithium and transition metal Material, such as LiCoO₂、LiNiO₂、LiMn₂O₄、LiCo_0.2Ni_0.2O₂、LiV₃O₈、LiNi_0.5Mn_1.5O₄、LiFePO₄、LiMnPO₄、 LiCOPO₄And LiVPO₄F.In other embodiments, these active material of cathode may include for example,

Li_aCoG_bO₂(0.90≤a≤1.8, and 0.001≤b≤0.1)；

Li_aNi_bMn_cCo_dR_eO_2-fZ_f, wherein 0.8≤a≤1.2,0.1≤b≤0.9,

0.0≤c≤0.7,0.05≤d≤0.4,0≤e≤0.2, the wherein summation of b+c+d+e are about 1, and 0≤f≤ 0.08；

Li_aA_1-b,R_bD₂(0.90≤a≤1.8 and 0≤b≤0.5)；

Li_aE_1-bR_bO_2-cD_c(0.90≤a≤1.8,0≤b≤0.5 and 0≤c≤0.05)；

Li_aNi_1-b-cCo_bR_cO_2-dZ_d, wherein 0.9≤a≤1.8,0≤b≤0.4,0≤c≤0.05, and 0≤d≤ 0.05；Or

Li_1+zNi_1-x-yCo_xAl_yO₂, wherein 0<x<0.3,0<y<0.1, and 0<z<0.06.

In the above chemical formula, A be Ni, Co, Mn, or combinations thereof；D be O, F, S, P, or combinations thereof；E be Co, Mn or its Combination；G be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or combinations thereof；R be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, rare earth element, or combinations thereof；Z be F, S, P, or combinations thereof.Suitable cathode and active material of cathode are included in United States Patent (USP) Numbers 5,962,166,6,680,145,6,964,828,7,026,070,7,078,128,7,303,840,7,381,496,7, 468,223,7,541,114,7,718,319,7,981,544,8,389,160,8,394,534 and 8,535,832, and Those of disclosed in reference paper therein." rare earth element " refers to the lanthanide series and Y and Sc from La to Lu.Another In a embodiment, which is NMC cathodes；That is, LiNiMnCoO cathodes.More precisely, wherein Ni:Mn:The atom of Co Than being 1:1:1(Li_aNi_1-b-cCo_bR_cO_2-dZ_d, wherein 0.98≤a≤1.05,0≤d≤0.05, b=0.333, c=0.333, Middle R includes Mn) or in which Ni:Mn:The atomic ratio of Co is 5:3:2(Li_aNi_1-b-cCo_bR_cO_2-dZ_d, wherein 0.98≤a≤1.05,0 ≤ d≤0.05, c=0.3, b=0.2, wherein R include Mn) cathode.

In another embodiment, which includes having formula Li_aMn_bJ_cO₄Z_dComposite material, wherein J is Ni, Co, Mn, Cr, Fe, Cu, V, Ti, Zr, Mo, B, Al, Ga, Si, Li, Mg, Ca, Sr, Zn, Sn, rare earth element, or combinations thereof；Z Be F, S, P, or combinations thereof；And 0.9≤a≤1.2,1.3≤b≤2.2,0≤c≤0.7,0≤d≤0.4.

In another embodiment, which includes showing in comparison Li/Li⁺Reference electrode is more than the potential model of 4.6V It is more than the active material of cathode of 30mAh/g capacity in enclosing.One example of such cathode is comprising containing with spinel structure Manganese cathode of the manganese composite oxide of lithium as the stabilization of active material of cathode.Contain lithium in being suitable for cathode as used herein Manganese composite oxide include have formula Li_xNi_yM_zMn_2-y-zO_4-dOxide, wherein x is 0.03 to 1.0；X is according to charging Release and absorption with lithium ion and electronics in discharge process and change；Y is 0.3 to 0.6；M include Cr, Fe, Co, Li, Al, It is one or more in Ga, Nb, Mo, Ti, Zr, Mg, Zn, V and Cu；Z is 0.01 to 0.18；And d is 0 to 0.3.Upper In one embodiment in formula, y is that 0.38 to 0.48, z is 0.03 to 0.12, and d is 0 to 0.1.A reality in above formula It applies in example, M is one or more in Li, Cr, Fe, Co and Ga.Stable manganese cathode can also include spinelle lamellar composite Material, these composite materials contain the layer structure of spinel components and rich lithium containing manganese, such as in U.S. Patent number 7,303,840 Described in.

In another embodiment, which includes by the composite material of the representation of following formula：

x(Li₂-wA_1-vQ_w+vO_3-e)·(1-x)(Li_yMn_2-zM_zO_4-d)

Wherein：

X is about 0.005 to about 0.1；

A includes one or more in Mn or Ti；

Q includes one or more in Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr or Y；

E is 0 to about 0.3；

V is 0 to about 0.5.

W is 0 to about 0.6；

M includes one kind or more in Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr or Y Kind；

D is 0 to about 0.5；

Y is about 0 to about 1；

Z is about 0.3 to about 1；And

The wherein Li_yMn_2-zM_zO_4-dComponent has spinel structure and the Li_2-wQ_w+vA_1-vO_3-eComponent has stratiform knot Structure.In one embodiment, x is about 0 to about 0.1.

In another embodiment, which includes active material of cathode, and the active material of cathode includes：

Li_aA_1-xR_xDO_4-fZ_f,

Wherein：

A be Fe, Mn, Ni, Co, V, or combinations thereof；

R be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, rare earth element, or combinations thereof；

D be P, S, Si, or combinations thereof；

Z be F, Cl, S, or combinations thereof；

0.8≤a≤2.2；

0≤x≤0.3；And

0≤f≤0.1。

In another embodiment, which includes active material of cathode, which is charged to comparison Li/ Li⁺Reference electrode is greater than or equal to about 4.0V, 4.1V, 4.2V, 4.3V, 4.35V, 4.40V, 4.45V, 4.5V, 4.55V or is more than The potential of 4.6V.Other examples are the stratiform-stratiform high power capacity oxygen evolution for the higher charged electric potential for being charged above 4.5V Cathode, such as in U.S. Patent number 7, those of described in 468,223.In one embodiment, which includes showing right Compare Li/Li⁺Reference electrode is more than the active material of cathode of 30mAh/g capacity or is electrically charged in the potential range more than 4.6V To comparison Li/Li⁺The active material of cathode of potential of the reference electrode more than or equal to 4.1V.

Before being suitable for active material of cathode as used herein and can using the hydroxide such as described by Liu et al. people Body method (physical chemistry periodical C (J.Phys.Chem.C) 13:It is prepared by method 15073-15079,2009).In the party In method, by adding KOH from the molten of the manganese containing required amount, nickel and other desirable one or more metal acetates Coprecipitated hydroxide precursor in liquid.Gained sediment is dried and then with the LiOHH of required amount₂O at about 800 DEG C extremely It is fired in oxygen at about 1000 DEG C and continues 3 to 24 hours.Alternatively, which can use such as special in the U.S. It is prepared by solid phase reaction process or sol-gel technology described in profit number 5,738,957.

The cathode (wherein the active material of cathode by comprising) can be prepared in the following manner：Make effective quantity (such as by Weight meter about 70% to by weight about 97%) active material of cathode and polymer adhesive (such as polyvinylidene fluoride) and Conductive carbon mixes in suitable solvent such as N-Methyl pyrrolidone to generate paste, and the paste is then coated to collector such as On aluminium foil, and it is dry to form the cathode.The weight percent is the total weight based on the cathode.

Electrochemical cell as in this disclosure further contains anode, and wherein the anode includes that can store and discharge lithium The active material of positive electrode of ion.The example of suitable active material of positive electrode includes for example, lithium alloy such as lithium-aluminium alloy, lithium-lead close Gold, lithium-silicon alloy, lithium-tin alloy；Carbon material such as graphite and mesophase-carbon micro-beads (MCMB)；Phosphorated material such as black phosphorus, MnP₄With And CoP₃；Metal oxide such as SnO₂, SnO and TiO₂；Nanocomposite containing antimony or tin, such as contain antimony, aluminium, titanium Or the oxide of molybdenum and the nanocomposite of carbon, such as by Yoon et al. (chemical materials (Chem.Mater.) 21,3898- 3904,2009) it is described those；And lithium titanate such as Li₄Ti₅O₁₂And LiTi₂O₄.In one embodiment, anode activity Material is lithium titanate or graphite.In another embodiment, which is graphite.In some embodiments, the anode activity material Material be lithium titanate, graphite, lithium alloy, silicon, or combinations thereof.

The anode can by with above for cathode description method class as method be made, wherein for example by adhesive Such as the copolymer based on vinyl fluoride is dissolved or dispersed in organic solvent or water, then by itself and active (conduction) material of anode Mixing is to obtain paste.The paste is coated in and needs to be used as on the metal foil preferably aluminium or copper foil of collector.Preferably With the heat drying paste so that the active material of positive electrode is bound on the collector.Suitable active material of positive electrode and anode It is to match this from such as Hitachi, Ltd of company (Hitachi), NEI companies (NEI Inc.) (Somerset, New Jersey) and farad Energy company (Farasis Energy Inc.) (Hayward, California) is commercially available.

The electrochemical cell is further contained in the porous septum between the anode and the cathode.The porous septum is for preventing The only short circuit between the anode and the cathode.The porous septum is typically by microporous polymer such as polyethylene, polypropylene, polyamides Amine, polyimides, or combinations thereof single-layer or multi-layer sheet material composition.The aperture of the porous septum is sufficiently large to allow to transmit Ion is contacted with the ionic conduction provided between the anode and cathode, but sufficiently small to prevent the anode and cathode from directly connecing Contact tactile or from the particle penetration or dendron that can be formed in the anode and cathode.It is suitable for porous septum as used herein Example be disclosed in U.S. Patent Application Publication No. 2012/0149852 (present U.S. Patent number 8,518,525).

Electrochemical cell disclosed here can be used for a variety of applications.It is deposited for example, the electrochemical cell can be used for power transmission network It stores up or is used as in the equipment (such as computer, camera, radio, electric tool) of the energy supply of various electronics or electron assistant, electricity Believe the power supply in equipment or transporting equipment (including motor vehicles, automobile, truck, bus or aircraft).Present disclosure also relates to And electronic equipment, telecommunication apparatus or transporting equipment comprising disclosed electrochemical cell.

Example

Concept disclosed here is illustrated in the following example.From described above and these examples, those skilled in the art It can determine the essential characteristic of concept disclosed here, and in the case of without departing from the spirit and scope, can make each Kind changes and changes to adapt to various uses and condition.

The meaning of used abbreviation is as follows：" DEG C " means degree Celsius；" g " means gram；" mg " means milligram；" μ g " means Microgram；" L " means to rise；" mL " means milliliter；" mol " means mole；" mmol " means mM；" M " means molar concentration； " wt% " means weight percent；" mm " means millimeter；" cm " means centimetre；" ppm " means parts per million；" h " means hour； " min " means minute；" s " means the second；" psi " means pound/square inch；" Pa " means Pascal；" A " means ampere；“mA” Mean milliampere；" mAh/g " mean Milliampere Hour/gram；" V " means volt；" rpm " means revolutions per minute；" NMR " means nuclear-magnetism Resonate spectral method；" GC/MS " means gas chromatography/mass spectrography；" Ex " means that example and " Comp.Ex " mean that comparison is real Example.

Material and method

The preparation of 2,2- bis-fluoro ethyls acetic acid esters (DFEA)

The 2,2- bis-fluoro ethyls acetic acid esters used in the following example is by making potassium acetate and HCF₂CH₂It is prepared by Br reactions 's.It is the exemplary program for the preparation below.

By potassium acetate (aldrich company (Aldrich), Milwaukee, Wisconsin State, 99%) at 100 DEG C Drying continues 4 to 5h under the vacuum of the Hg (66.7-133Pa) of 0.5-1mm.There is the material of the drying water less than 5ppm to contain Amount, as determined by karr-Karl Fischer titration.In drying box, by the drying of 212g (2.16mol, 8mol% are excessive) Potassium acetate place to containing weight magnetic stirring bar 1.0-L three neck round bottom in.The flask is removed from the drying box, It is transferred in draught cupboard, and is equipped with thermocouple sheath, dry-ice condenser and additional funnel.

By sulfolane, (500mL, aldrich company, 99%, 600ppm water are such as determined by karr-Karl Fischer titration ) melting and be added in three neck round bottom as liquid under nitrogen flowing.Start to stir and make the temperature of reaction medium Reach about 100 DEG C.By HCF₂CH₂Br (290g, 2mol, E.I.Du Pont Company (E.I.du Pont de Nemours and Co.), 99%) it is positioned in charging hopper, and is added slowly in the reaction medium.The addition is mild exothermic, and is being added Increasing in the 15-20min after beginning makes the temperature of the reaction medium rise to 120 DEG C -130 DEG C.By HCF₂CH₂The addition of Br is maintained at Internal temperature is maintained under the rate at 125 DEG C -135 DEG C.The addition expends about 2-3h.By the reaction medium 120 DEG C- It is stirred at 130 DEG C and continues additional 6h (typically the conversion ratio of bromide is about 90%-95% at this time).Then, by the reaction Medium is cooled to room temperature and is stirred overnight.The next morning restarts another heating and continuous 8h.

At this point, starting bromide is undetectable by NMR, and crude reaction medium contains the 1 of 0.2%-0.5%, 1- difluoroethanols.Dry-ice condenser on the reaction flask by withThe hose adapter of valve is replaced, and should Flask is connected to by cold-trap (- 78 DEG C, dry ice/acetone) on oil-sealed rotary pump.The reaction product is transferred in 1-2mm Hg In cold-trap under the vacuum of (133 to 266Pa) at 40 DEG C -50 DEG C.The transfer expends about 4-5h and leads to 220-240g's The thick HCF of about 98%-98.5% purity₂CH₂OC(O)CH₃, the substance is by a small amount of HCF₂CH₂Br (about 0.1%-0.2%), HCF₂CH₂OH (0.2%-0.8%), sulfolane (about 0.3%-0.5%) and water (600-800ppm) pollution.

Being further purified for the crude product is carried out using Spinning Band Distillation under atmospheric pressure.Collect have 106.5 DEG C- The fraction and use GC/MS (capillary column HP5MS, phenyl-methyl silicone, Agilent of boiling point between 106.7 DEG C 19091S-433,30m, 250 μm, 0.25 μm；Carrier gas-He, flow velocity 1mL/min；Temperature program(me)：40 DEG C, 4min, temperature slope 30 DEG C/min, and 230 DEG C, 20min) monitoring Impurity Distribution.Typically, the distillation of 240g crude products provides the 99.89% pure of about 120g The HCF of degree₂CH₂OC(O)CH₃(the H of 250-300ppm₂O) and the material of 99.91% purity of 80g (contains about 280ppm's Water).It goes to remove water from product of distillation by being handled with 3A molecular sieves, until water is undetectable by karr-Karl Fischer titration (that is,≤1ppm).

The purifying of bis- (oxalic acid) lithium borates

In the drying box of nitrogen purging, bis- (oxalic acid) lithium borate (LiBOB, Sigmas-Order are purified by following procedure Ritchie company (Sigma-Aldrich), Milwaukee, Wisconsin State).By the LiBOB of 11.25g be added to 50mL without In the beaker of the 400mL of water-acetonitrile.The mixture is stirred and heated to 40 DEG C and lasts about 30 minutes.The mixture of warm is led to The filtering of Whatman#1 filters is crossed, is transferred in second beaker and allows to cool to room temperature；Obtain clear solution.It is clear to this The cold dry toluenes of about 50mL (- 30 DEG C) are added in clear solution.Be stirred for persistently additional 30 minutes to form sediment.It should Solution is filtered by Whatman#1 filters and washs filter cake with cold dry toluene.Make the filter cake in vacuum filter funnel After upper drying, by solid from the vacuum drying oven for removing, being positioned at 130 DEG C in drying box, and blown with slight nitrogen It sweeps drying and continues 15 hours to obtain the LiBOB of purifying, then handle it in the drying box of nitrogen purging.

Example 1 and example 2

Comparison example A, B and C

It is prepared by representative cathode

LiMn_1.5Ni_0.45Fe_0.05O₄(Fe-LNMO) prepared by the representative of active material of cathode

It is the typical case for being used to prepare the active material of cathode used in example 1 and 2 and comparison example A, B and C below Program.For LiMn_1.5Ni_0.45Fe_0.05O₄Preparation, by 401g manganese acetates (II) tetrahydrate, (aldrich company, Mill are fertile Base, Wisconsin State, production number 63537), 125g nickel acetates (II) tetrahydrate (aldrich company, production number 72225) and 10g anhydrous acetic acids iron (II) (AlfaAesar company (Alfa Aesar), Ward mountain, the South Dakota State, production number 31140) is weighed In bottle on to balance, it is then dissolved in 5.0L deionized waters.By KOH pellet dissolutions in 30L in 10L deionized waters 3.0M solution is generated in reactor.Solution containing metal acetate is transferred in charging hopper and instill quickly stir it is anti- Hydroxide materials precipitation so that mixed is answered in device.Once the metal acetate solutions of all 5.0L are added to the reactor In, continue to stir lasting 1h.Then, stop stirring and make sediment sedimentation overnight.After sedimentation, it is removed from the reactor Liquid, and add the fresh deionized waters of 15L.The content of the reactor is stirred, so that it is settled again, and remove liquid. Repeat this flushing process.Then, which is transferred to useTwo (dividing equally) raw glass material mistakes of paper covering It filters in funnel.These solids are rinsed with deionized water until filtrate pH reaches 6.0 (pH of deionization flushing water), and to each filter Other 20L deionized waters are added in cake.Finally, it is dried overnight in the vacuum drying oven by cake at 120 DEG C.Yield at this time is typical Ground is 80%-90%.

The hydroxide sediment is ground and is mixed with lithium carbonate.Use the automatic mortars of Pulverisette and pestle (not Ritchie company (FRITSCH), Germany) completes this step with 50g in batches.For every batch of, the hydroxide sediment of weighing, Then it is individually ground in Pulveresette and continues 5min.Then, the lithium carbonate of a small amount of excessive stoichiometric amount is added Into the system.For 50g hydroxide sediments, 10.5g lithium carbonates are added.Continue grinding and continue 60min in total, wherein often 10-15min stops with the surface scrape material with sharp metal spatula from the mortar and pestle.If humidity leads to material shape At agglomerate, then it by the sieve of 40 mesh sieve once in process of lapping, then be sieved again after grinding.

The material of grinding is fired in shallow rectangular alumina disk in air batch-type furnace.These disk sizes be 158mm × 69mm, and each keep the material of about 60g.The firing program in 15h from room temperature to 900 DEG C, at 900 DEG C by keeping Continue 12h and then is cooled to room temperature composition in 15h.

After firing, by the powder ball milling to reduce granularity.Then, by 54g powder and 54g isopropanols and 160g The zirconium oxide bead of 5mm diameters is in polyethylene tank internal mix.Then by the tank in a pair of rolls rotation lasts 6h to grind.Pass through The slurry is centrifuged, and the powder is dried at 120 DEG C to remove moisture removal.

Using polyimides/carbon composite priming paint is prepared on aluminium foil collector

It is the exemplary program for the priming paint being used to prepare on the aluminium foil collector used in example and comparison example below.For It prepares polyamic acid, prepares prepolymer first.Use the 0.98 of stoichiometric amount:1 PMDA/ODA (pyromellitic acid dianhydride // ODA (4,4'- diamino-diphenyls ether) prepolymer) prepare the PMDA of 20.6wt10%:ODA prepolymers.This is by mildly stirring It mixes down that ODA is dissolved in N-Methyl pyrrolidone (NMP) in about 45 minutes processes at room temperature and prepares.It will PMDA powder is added slowly in the mixture (with small equal portions) to control the raising of any temperature in the solution；It is small about 2 When it is interior carry out PMDA addition.It is added under controlled temperature condition and stirs acquired solution.Polyamic acid it is final dense Degree is that the molar ratio of 20.6wt% and acid anhydrides and amine component is about 0.98:1.In a separate container, by by 1.00g's The NMP (N-Methyl pyrrolidone) of PMDA (Aldrich 412287, Alan town, Pennsylvania) and 15.67g combines to make Pyromellitic dianhydride (PMDA) solution of standby 6wt%.4.0 grams of PMDA solution are added slowly to increase in the prepolymer and by viscosity Add to about 90,000 pools (as by 25 viscosimeter-#6 rotor measurements of Bu Shi).This leads to final pre-polymer solution, falls into a trap The final PMDA calculated:ODA ratios are 1.01:1.Then 5.196 grams of final prepolymers, 15.09 grams of NMP are diluted to generate 5wt% solution.In the vial, 16.2342 grams of diluted final pre-polymer solutions are added to 0.1838 gram of TimCal 30 In Super C-65 carbon blacks.By it, with 9.561 grams of NMP, further dilution has to reach the final solid content of 3.4wt% 2.72 prepolymer:Carbon ratio.Paasche VL#3 Airbrush sprayers (Pa She spray guns company (Paasche Airbrush Company), Chicago, Illinois) for by the material spray to aluminium foil (25 μ m-thicks, 1145-0, Allfoils companies, Brooklyn Heights, Ohio) on.The foil is weighed before the spraying, and 0.06mg/cm is reached with the necessary coating of determination²Institute Desired density.Then so that the foil is smoothed on glass plate, and manually use gun spraying until coating.Then by the foil in heat It is dry at 125 DEG C on plate, and measure to ensure to reach desirable density.It was found that the foil is coated with 0.06mg/cm²Polyamides Amino acid.Once the foil is dried and is in desirable coating, which follows following imidizate program by acyl at 400 DEG C Imidization：

40 DEG C to 125 DEG C (with the slopes of 4 DEG C/min)

125 DEG C to 125 DEG C (impregnating 30min)

125 DEG C to 250 DEG C (with the slopes of 4 DEG C/min)

250 DEG C to 250 DEG C (impregnating 30min)

250 DEG C to 400 DEG C (with the slopes of 5 DEG C/min)

400 DEG C to 400 DEG C (impregnating 20min).

The preparation of paste

It is the exemplary program for being used to prepare cathode below.Adhesive is as polyvinylidene fluoride in N-Methyl pyrrolidone 5.5% solution (5130 (Su Wei companies, Houston, Texas)) it obtains.Following material is for manufacturing electrode Paste：LiMn as prepared above 4.16g_1.5Ni_0.45Fe_0.05O₄Cathode active powder；0.52g carbon blacks (unpressed Denka, Electrochemically company (DENKA Corp.), Japan)；PVDF (polyvinylidene fluoride) solution of 4.32g；And 7.76g+1.40g NMP (Sigma-Aldrich).As described below, by these materials with 80:10:10 cathode active powders:PVDF: The ratio combine of carbon black.Final paste contains 28.6% solid.

NMP the and PVDF solution of carbon black, first part is combined in plastic jar first, and is eccentrically mixed (ARE-310, Thinky companies of the U.S., La Guaira mountain, California) twice, continues 60s with 2000rpm every time.Addition The NMP of the cathode active powder and second part, and twice (2 × 1min at 2000rpm) by paste centrifugation mixing.It will The bottle is positioned in ice bath, and (model PT 10-35GT, 7.5mm diameter stators, Kinematicia, wave are uncommon by homogenizer Meter Ya, New York) rotor-stator axis be inserted into the bottle.Between being wrapped between the top of the bottle and the stator with aluminium foil Gap into the water in the bottle so as to minimize.Twice by gained paste homogenizing, 15min is continued with 6500rpm every time, and so It is homogenized again afterwards twice, 15min is continued with 9500rpm every time.Between each in four homogenising time sections, by the homogenizer It is moved to another position in the paste bottle.

It is used with 0.41-0.51mm using automatic coating device (AFA-II, MTI company, Richmond, California) The paste is cast to aluminium foil (25 μ m-thicks, 1145-0, Allfoils companies, Brooklyn Heights, E Hai by the scraper for pouring open height Russia state) on.By electrode in mechanical convection baking oven (model FDL-115, adhesive Co., Ltd (Binder Inc.), great river (Great River), New York) in dry at 95 DEG C continue 30min.The cathode of gained 51-mm wide is placed on 125mm thickness Between brass sheet material and at ambient temperature three times by using the calender of the steel rider of 100mm diameters, wherein passing through every time Middle roll gap power increases, begun through at 260kg and at 770kg eventually by.The load capacity of active material of cathode be 7 to 8mg/cm²。

It is prepared by representative anode

It is the exemplary program for being used to prepare anode below.By following material preparation anode paste：5.00g graphite (G5, Concophillips Company (Conoco-Philips), Houston, Texas)；0.2743g carbon blacks (Super C65, Te Migao company (Timcal), Westlake, Ohio)；3.06g PVDF (in NMP 13%, KFL#9130, Wu Yu companies of the U.S. (Kureha America Corp.))；The 1-Methyl-2-Pyrrolidone (NMP) of 11.00g；And 0.0097g oxalic acid (Sigma-Aldrich company,>99% purity).As described below, by these materials with 88: 0.17:7:4.83 graphite:Oxalic acid:PVDF:The ratio combine of carbon black.Final paste contains 29.4% solid.

Oxalic acid, carbon black, NMP and PVDF solution are combined in plastic jar.Using planetary centrifugal mixer by these Material is mixed at 2000rpm continues 60s.The mixing is repeated for the second time.Then graphite is added.By gained paste centrifugation mixing two It is secondary.The bottle is mounted in ice bath and is homogenized twice using rotor-stator, 15min is continued with 6500rpm every time, and Then it is homogenized again twice, 15min is continued with 9500rpm every time.Wherein stator axis enter the bottle point with aluminium foil wrap up so that Vapor into the bottle minimizes.Between each in four homogenising time sections, which is moved to the paste Another position in agent bottle.Then three times by paste centrifugation mixing.

Being used using automatic coating device, there are 230 μm of scrapers for pouring open height the paste is cast to copper foil (CF-LBX- 10, Feitian company (Fukuda), capital of a country, Japan) on.It is these electrodes are dry at 95 DEG C in mechanical convection baking oven to continue 30min.The anode of gained 51-mm wide is placed between the brass sheet material of 125 μ m-thicks and at ambient temperature by using The calender of the steel rider of 100mm diameters three times, wherein every time by middle roll gap power increase, begun through at 260kg and At 770kg eventually by.The load capacity of active material of positive electrode is 3 to 4mg/cm²。

It is prepared by electrolyte

For example 1, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls acetic acid esters of 70 weight percent Ethylene carbonate (EC, BASF AG, independent city, the Russia of (DFEA, as being described herein preparation above) and 30 weight percent Last of the twelve Earthly Branches Russia state) it combines to prepare the electrolyte composition.Add molecular sieve (3A) and by the mixture is dry to less than 1ppm water. After being filtered with 0.25 micron PTFE syringe device formula filter, enough LiPF are added₆With manufacture 1M in LiPF₆In match Product.By 2 (5H)-furanones (Sigma-Aldrich company, 98% purity) (its of the mixture of 1.96g and 0.04g Filtered by the alumina filled syringe with 0.2 micron PTFE filter being attached on end) it combines to produce Raw final electrolyte composition.

For example 2, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls acetic acid esters of 70 weight percent It is combined with the ethylene carbonate of 30 weight percent to prepare the electrolyte composition.Add molecular sieve (3A) and by the mixing Object drying to less than 1ppm water.After being filtered with 0.25 micron PTFE syringe device formula filter, enough LiPF are added₆With system Make 1M in LiPF₆In preparation.By 2 (the 5H)-furanones of the mixture of 1.92g and 0.04g, (it is by having Be attached to the alumina filled syringe filtering of 0.2 micron PTFE filter on end) and 0.04g purifying LiBOB It is combined to produce final electrolyte composition.

For comparison example A, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls second of 70 weight percent The ethylene carbonate of acid esters and 30 weight percent combines to prepare the electrolyte composition.Add molecular sieve (3A) and should Mixture drying to less than 1ppm water.After being filtered with 0.25 micron PTFE syringe device formula filter, enough LiPF are added₆ (lithium hexafluoro phosphate, BASF AG, independent city, Ohio) with manufacture 1M in LiPF₆In final electrolyte composition.

For comparison example B, by the drying box that nitrogen purges by the methyl ethyl carbonate of 70 weight percent (EMC, BASF AG, independent city, Ohio) and the ethylene carbonate of 30 weight percent combine and prepare the electrolyte combination Object.Add molecular sieve (3A) and by the mixture is dry to less than 1ppm water.With 0.2 micron PTFE syringe device formula filter After filtering, enough LiPF are added₆With manufacture 1M in LiPF₆In preparation.By the mixture of 1.96g and 0.04g (it passes through the alumina filled injection with 0.2 micron PTFE filter being attached on end to 2 (5H)-furanones Device filters) it is combined to produce final electrolyte composition.

For comparison example C, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls second of 70 weight percent The ethylene carbonate of acid esters and 30 weight percent combines to prepare the electrolyte composition.Add molecular sieve (3A) and should Mixture drying to less than 1ppm water.After being filtered with 0.25 micron PTFE syringe device formula filter, enough LiPF are added₆ With manufacture 1M in LiPF₆In preparation.By gamma-butyrolacton (GBL, Sigma-Austria of the mixture of 1.96g and 0.04g The strange company in Delhi, 98% purity) it combines to prepare final electrolyte composition.

Button cell manufactures

The cathode of the circular anode of 14.3mm diameters and 12.7mm diameters is rushed from electrode sheet described herein above It extrudes, being placed on glove box, (vacuum atmosphere company (Vacuum Atmospheres), Huo Sang, California have HE- 493 clarifiers) cup in heater in, be further dried overnight at 90 DEG C in a vacuum, and enter argon gas fill Glove box in.Non-aqueous electrolyte lithium ion CR2032 button cells are prepared for electrochemical evaluation.Button cell part (shell, gasket, waveform spring, washer and lid) and button cell curler are obtained from Hohsen companies (Osaka, Japan).Every Film is(the carga moral/Polypore international corporations (Celgard/Polypore of single layer PP battery packs diaphragm 2500 International), Xia Luote, the North Carolina state).

In 55 DEG C of lower button cell evaluations

Three kinds are manufactured using each electrolyte composition of example 1, comparison example A, comparison example B and comparison example C Button cell, in total 12 batteries.Two kinds of button cells are manufactured using the electrolyte composition of example 2.Use business electricity Pond group tester (4000 series, Maccor companies, Tulsa, Russia carat He Ma Zhou) is used at ambient temperature in 3.4- Constant current charge and electric discharge between the voltage limitation of 4.9V and the cathode activity using the constant current (CC) of 12mA per g Material makes all these button cell cycles be used to be melted into twice.

After being melted into program, these batteries are placed in the baking oven at 55 DEG C, and use the electricity in 3.4-4.9V (it is about that 2C multiplying powers are held in the electric current of every gram of active material of cathode 240mA for constant current charge and electric discharge between pressure limitation Continuous 250 cycles) under recycle.

As a result be summarised in table 1, the table provide used in solvent and additive, measure in the first chemical conversion cycle Coulombic efficiency (CE), the CE in the tenth cycle and the discharge capacitance at 55 DEG C under 250 cycles.Coulomb effect Rate is defined as (discharge capacity)/(charging capacity).Discharge capacitance under being recycled at 250 times is as such as manufacture original sample The percentage of battery capacity provides.By the way that the quality of active material of cathode is multiplied by 120mAh/g, (it is active material of cathode The capacity of quality standardization) come calculate as manufacture original sample battery capacity.

The coulombic efficiency and discharge capacitance data of button cell cycle of the table 1. at 55 DEG C

Annotation：

¹All electrolyte compositions also contain 1M LiPF in a solvent₆

²" NA " means " not applicable " -- battery does not recycle

Result in table 1 demonstrates, and does not such as have 2 (5H)-furanone additives with identical solvent blend is used The battery of (comparison example A) still has non-fluorinated solvents blend (comparison example using 2 (5H)-furanone additives B battery) is compared, and is provided using 2 (5H)-furanones as electrolyte additive (example 1) with the capacity greatly improved The electrochemical cell of conservation rate and coulombic efficiency.2 (5H)-furanones and LiBOB are combined into (example 2) with same solvent blend Additionally provide the electrochemical cell with improved capacity retention ratio and coulombic efficiency such as compared with comparison example A.Comparison example C It shows, replaces unconjugated gamma-butyrolacton to be provided (instead of 2 (5H)-furanones of conjugation) with identical solvent blend The electrochemical cell-not recycled apparent poor result compared with those of example 1.

Example 3

Comparison example D

It is prepared by the representative of the cathode containing NMC (532) active material of cathode

It is the exemplary program for being used to prepare the cathode used in example 3 and comparison example D below.Adhesive is prepared into Polyvinylidene fluoride (Solef^TM5130 (Su Wei companies, Houston, Texas)) in N-Methyl pyrrolidone (Sigma- Aldrich company) in 5% solution.Following material is for manufacturing electrode paste agent：9.36g LiNi_0.5Mn_0.3Co_0.2O₂It is cloudy Pole reactive powder；0.52g carbon blacks (Super C65 (Te Migao companies)；PVDF (polyvinylidene fluoride) solution of 10.4g and The NMP (Sigma-Aldrich company) of 3.0g.As described below, by these materials with 90:5:5 cathode active powders: PVDF:The weight rate of carbon black combines.

NMP the and PVDF solution of carbon black, extention is combined in the vial, and centrifuges mixing (ARE-310, the U.S. Thinky companies, La Guaira mountain, California) twice, 60s is continued with 2000rpm every time.Cathode active powder is added, And twice (2 × 1min at 2000rpm) by paste centrifugation mixing.By homogenizer, (model PT 10-35 GT, 7.5mm is straight Diameter stator, Kinematicia, bohemia, New York) rotor-stator axis be inserted into bottle, and gained paste is homogenized, 5min is continued with 9500rpm every time.Then the paste is continued into 1min at 2000rpm by centrifuging mixing degassing.

It is used with 0.290mm cast gates using automatic coating device (AFA-II, MTI company, Richmond, California) The paste is cast to aluminium foil (25 μ m-thicks, 1145-0, Allfoils companies, Brooklyn Heights, Ohio by the scraper of height State) on.By electrode in mechanical convection baking oven (model FDL-115, adhesive Co., Ltd, great river, knob with temperature slope Dried in about) and with since 80 DEG C -100 DEG C of 15min slopes keep, followed by 100 DEG C keep.Cathode is placed on Between the stainless steel sheet material of 0.5mm thickness and at 125 DEG C three times by using the calender of the steel rider of 100mm diameters, wherein Every time by middle roll gap power increase, begun through at 9psig and at 30psig terminate eventually by.

The load capacity of active material of cathode is about 14.8mg/cm²。

It is prepared by representative anode

It is the exemplary program for being used to prepare the anode such as used in example 3 and comparison example D below.By following material system Standby anode paste：6.2062g graphite (G5, Concophillips Company, Houston, Texas)；0.3406g charcoals Black (Super C65, Te Migao companies, Westlake, Ohio)；PVDF (in NMP 13%, the KFL# of 3.7975g 9130, Wu Yu companies of the U.S.)；13.0974g 1-Methyl-2-Pyrrolidone (NMP)；And 0.0119g oxalic acid.It is retouched Ru following It states, by these materials with 88:0.17:7:4.83 graphite:Oxalic acid:PVDF:The weight rate of carbon black combines.Final paste contains There is 29.4% solid.

Oxalic acid, carbon black, half NMP and PVDF solution are combined in plastic jar.It will using planetary centrifugal mixer These materials are mixed at 2000rpm continues 60s.The mixing is repeated for the second time.Then graphite is added together with remaining NMP Enter.Twice by gained paste centrifugation mixing.Bottle is homogenized by lasting 5min with 10,000rpm using rotor-stator, adjusts bottle Position in entire mixing.Then bottle is remixed into lasting 60s at 2000rpm.

Being used using automatic coating device, there are 290 μm of scrapers for pouring open height the paste is cast to copper foil (CF-LBX- 10, Feitian company (Fukuda), capital of a country, Japan) on.It is these electrodes are dry at 95 DEG C in mechanical convection baking oven to continue 30min.The anode of gained 102-mm wide is placed between the stainless steel sheet material (being layered with the sheet material of Kapton) of 390 μ m-thicks And by using the calender of the steel rider of 100mm diameters (being maintained at 125 DEG C) four times, wherein increasing passing through middle roll gap power every time Adduction and by film approach axis move 180 °, begun through at 340kg and at 1130kg eventually by.

The load capacity of active material of positive electrode is about 8.4mg/cm²

It is prepared by electrolyte

For comparison example D, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls second of 70 weight percent The ethylene carbonate (EC, BASF AG, independent city, Ohio) of acid esters and 30 weight percent combines to prepare the electrolysis Matter composition.Add molecular sieve (3A) and by the mixture is dry to less than 1ppm water.With 0.25 micron PTFE syringe device After the filtering of formula filter, enough LiPF are added₆With manufacture 1M in LiPF₆In preparation.

For example 3, by the drying box that nitrogen purges by 2, the 2- bis-fluoro ethyls acetic acid esters of 70 weight percent It is combined with the ethylene carbonate of 30 weight percent to prepare the electrolyte composition.Add molecular sieve (3A) and by the mixing Object drying to less than 1ppm water.After being filtered with 0.25 micron PTFE syringe device formula filter, enough LiPF are added₆With system Make 1M in LiPF₆In preparation.By 2 (the 5H)-furanones and 0.04g ethyl sulfates of the 1.92g mixtures and 0.04g (ES) it is combined to produce final electrolyte composition.Before the use, which is attached to end by having The alumina filled syringe filtering of 0.2 micron PTFE filter on end；By the ethyl sulfate (in Sigma-Order Strange company) it is purified by vacuum sublimation.

Button cell manufactures

It will stamp out in the electrode sheet of the cathode of the circular anode of 14.3mm diameters and 12.7mm diameters from the above description, The heater being placed in the cup of glove box (vacuum atmosphere company, Huo Sang, California, with HE-493 clarifiers) In, it is further dried overnight at 90 DEG C in a vacuum, and enter in the glove box of argon gas filling.Prepare non-aqueous electrolyte Lithium ion CR2032 button cells are used for electrochemical evaluation.Button cell part (shell, gasket, waveform spring, washer and lid) and Button cell curler is obtained from Hohsen companies (Osaka, Japan).Diaphragm is Celgard single layer PP battery pack diaphragms 2500 (carga moral/Polypore international corporations (Celgard/Polypore International), Xia Luote, northern Caros The states Lai Na).

In 45 DEG C of lower button cell evaluations

Three kinds of button cells, total of six electricity are manufactured using each electrolyte composition of example 3 and comparison example D Pond.Button cell is charged with 0.25C multiplying powers initially and continues 36min, followed by static 12h.Then proceed to charging one for the first time Until 4.35V (wherein constant voltage is maintained at C/20 cut-offs), continue 10min followed by static, and then transferred in 0.5C Electricity is until 3.0V.Second of cycle is static by 10min, (is wherein maintained at up to 4.35V followed by the charging of 0.2C multiplying powers Under 4.35V) and 0.05C multiplying powers cut-off composition.Subsequent static 10min and then with 0.2C multiplying power dischargings to 3.0V.Use quotient Industry battery pack tester (4000 series, Maccor companies, Tulsa, Russia carat He Ma Zhou) carries out chemical conversion journey at ambient temperature Sequence.

After being melted into program, these batteries are placed in the baking oven at 45 DEG C, and use the electricity in 3.0-4.35V Constant current charge between pressure limitation and electric discharge, using in the electric current of every gram of active material of cathode 170mA, (it is about 1C times Rate) under 19 cycles, followed followed by the iteration scheme of 1 time under the electric current (it is about 0.2C multiplying powers) of 34mA/g cycle Ring.Lasting 120 cycles are repeated in this way.

As a result be summarised in table 2, the table indicate used solvent and additive, at 45 DEG C 110 times cycle under Discharge capacitance, average discharge capacity conservation rate, at 110 times recycle under coulombic efficiency and at 110 times recycle under Average coulombic efficiency.Discharge capacitance under being recycled at 250 times is given as the percentage of such as battery capacity of manufacture original sample Go out.By by the quality of active material of cathode be multiplied by 170mAh/g (it is the capacity of the quality standardization of active material of cathode) come Calculate the capacity of the battery such as manufacture original sample.

The discharge capacitance and coulombic efficiency data of button cell cycle of the table 2. at 45 DEG C

Annotation：

¹All electrolyte compositions also contain 1M LiPF in a solvent₆

Result in table 2 shows, as with use identical solvent blend and without additive (comparison example D) Battery is compared, and solvent blend and 2 (5H)-furans containing 70,/30 2,2- bis-fluoro ethyls acetic acid esters/ethylene carbonate are used Both ketone and ethyl sulfate are provided as the electrolyte composition (example 3) of additive and are kept with the capacity greatly improved The electrochemical cell of rate and improved coulombic efficiency.

Claims (30)

1. a kind of electrolyte composition, including：

A) fluorated solvent；

B) carbonic ester cosolvent；

C) at least one gamma lactone indicated by formula (II)

Wherein

R⁷、R⁸、R⁹And R¹⁰Be each independently H, F, linear chain or branched chain C₁To C₁₀The C of alkyl or linear chain or branched chain₁To C₁₀Fluorine Alkyl；With

D) at least one electrolytic salt.

2. electrolyte composition as described in claim 1, the wherein fluorated solvent are：

A) the fluorinated non-annularity carboxylate being expressed from the next

R¹-COO-R²,

B) the fluorinated non-cyclic carbonate being expressed from the next

R³-OCOO-R⁴,

C) by formula R⁵-O-R⁶Or mixtures thereof the fluorinated non-annularity ether indicated,；

Wherein

i)R¹It is H, alkyl or fluoroalkyl；

ii)R³And R⁵It is fluoroalkyl each independently and can be same or different to each other；

iii)R²、R⁴And R⁶It is alkyl or fluoroalkyl each independently and can be same or different to each other；

iv)R¹And R²Any one of or both include fluorine；And

V) respectively as a pair of R¹And R²、R³And R⁴And R⁵And R⁶Including at least two carbon atoms but be no more than seven carbon originals Son.

3. electrolyte composition as claimed in claim 2, wherein respectively as a pair of R¹And R²、R³And R⁴And R⁵And R⁶ At least two fluorine atoms are further included, condition is R¹、R²、R³、R⁴、R⁵And R⁶- CH is not all contained₂F or-CHF- groups.

4. electrolyte composition as claimed in claim 2, the wherein fluorated solvent are fluorinated non-annularity carboxylates.

5. electrolyte composition as claimed in claim 4, wherein the fluorinated non-annularity carboxylate is CH₃-COO-CH₂CF₂H、 CH₃CH₂-COO-CH₂CF₂H、F₂CHCH₂-COO-CH₃、F₂CHCH₂-COO-CH₂CH₃、CH₃-COO-CH₂CH₂CF₂H、CH₃CH₂- COO-CH₂CH₂CF₂H、F₂CHCH₂CH₂-COO-CH₂CH₃、CH₃-COO-CH₂CF₃、CH₃CH₂-COO-CH₂CF₂H、H-COO- CH₂CF₂H、H-COO-CH₂CF₃Or mixtures thereof,.

6. electrolyte composition as claimed in claim 4, wherein the non-annularity carboxylate include 2,2- bis-fluoro ethyls acetic acid esters.

7. electrolyte composition as claimed in claim 2, the wherein fluorated solvent are fluorinated non-cyclic carbonates.

8. electrolyte composition as claimed in claim 7, the wherein fluorinated non-cyclic carbonate are methyl 2,2- difluoro second Base carbonic ester；Methyl 2,2,2- trifluoroethyl carbonic esters；Methyl 2,2,3,3- tetrafluoro propyl carbonates；2,2- bis-fluoro ethyls ethyls Carbonic ester；2,2,2- trifluoroethyl ethyl carbonate esters；Or mixtures thereof.

9. electrolyte composition as described in claim 1, wherein the carbonic ester cosolvent include nonfluorinated carbonic ester.

10. electrolyte composition as claimed in claim 9, wherein the nonfluorinated carbonic ester include ethylene carbonate, carbonic acid Asia Propyl ester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, dimethyl dicarbonate butyl ester, dipropyl carbonate, carbon Sour first propyl ester, carbonic acid ethyl propyl vinylene, carbonic acid first butyl ester, ethyl butyl carbonate, the third butyl ester of carbonic acid, dibutyl carbonate, carbon Or mixtures thereof sour vinyl ethyl, carbonic acid dimethyl vinylene.

11. electrolyte composition as described in claim 1, wherein the carbonic ester cosolvent include fluorocarbons acid esters.

12. electrolyte composition as claimed in claim 11, wherein the fluorocarbons acid esters include that fluoro- 1, the 3- dioxies rings of 4- are amyl- 2- ketone；The bis- amyl- 2- ketone of fluoro- 1,3- dioxies ring of 4,5-；The bis- amyl- 2- ketone of fluoro- 4- methyl-1,3-dioxies ring of 4,5-；4,5- bis- fluoro- 4, The amyl- 2- ketone of 5- dimethyl -1,3- dioxy rings；The bis- amyl- 2- ketone of fluoro- 1,3- dioxies ring of 4,4-；Tri- fluoro- 1,3- dioxies rings of 4,4,5- Amyl- 2- ketone；Or mixtures thereof.

13. electrolyte composition as described in claim 1, the wherein fluorated solvent include 2,2- bis-fluoro ethyls acetic acid esters；2, 2- bis-fluoro ethyls methyl carbonics；Or mixtures thereof.

14. electrolyte composition as described in claim 1, the wherein gamma lactone include 2 (5H)-furanones.

15. electrolyte composition as described in claim 1, wherein the total weight based on the electrolyte composition, the electrolyte Composition includes the gamma lactone of about 0.1 weight percent to about 5 weight percent.

16. electrolyte composition as described in claim 1 further includes the cyclic sulfates indicated by formula (III)

Wherein each Q is independently hydrogen or optionally fluorinated vinyl, allyl, alkynyl, propargyl or C₁-C₃Alkyl.

17. electrolyte composition as claimed in claim 16, the wherein cyclic sulfates include ethyl sulfate.

18. electrolyte composition as described in claim 1 further includes at least one component selected from the following terms：

I) borate indicated by formula (IV)：

LiBF_(4-2p)(C₂O₄)_p (IV)

Wherein p is 0,1 or 2；And/or

Ii) the oxalates indicated by formula (V)：

LiPF_(6-2q)(C₂O₄)_q (V)

Wherein q is 1,2 or 3.

19. electrolyte composition as claimed in claim 18, the wherein borate include bis- (oxalic acid) lithium borates.

20. electrolyte composition as claimed in claim 18, the wherein oxalates include three (oxalic acid) lithium phosphates.

21. a kind of electrochemical cell, including：

(a) shell；

(b) it is disposed in the anode and cathode that in the shell and ionic conduction contacts each other；

(c) be disposed in the shell and provide the ionic conduction access between the anode and the cathode such as claim Electrolyte composition described in 1；With

(d) porous septum between the anode and the cathode.

22. electrochemical cell as claimed in claim 21, the wherein electrochemical cell are Li-ion batteries piles.

23. electrochemical cell as claimed in claim 22, the wherein anode include active material of positive electrode, and anode activity Material be lithium titanate, graphite, lithium alloy, silicon, or combinations thereof.

24. electrochemical cell as claimed in claim 22, the wherein cathode include showing in comparison Li/Li⁺Reference electrode is big In the active material of cathode for being more than 30mAh/g capacity in the potential range of 4.6V or it is charged to comparison Li/Li⁺Reference electricity The active material of cathode of potential of the pole more than or equal to 4.1V.

25. electrochemical cell as claimed in claim 22, the wherein cathode include active material of cathode, and the cathode activity Material includes

Li_aNi_bMn_cCo_dR_eO_2-fZ_f,

Wherein：

R be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, rare earth element, or combinations thereof；

Z be F, S, P, or combinations thereof；And

0.8≤a≤1.2、0.1≤b≤0.9、0.0≤c≤0.7、0.05≤d≤0.4、0≤e≤0.2；Wherein b+c+d+e's Summation is about 1；And 0≤f≤0.08.

26. electrochemical cell as claimed in claim 22, the wherein cathode include active material of cathode, and the cathode activity Material includes by the composite material of the representation with following formula：

x(Li_2-wA_1-vQ_w+vO_3-e)·(1-x)(Li_yMn_2-zM_zO_4-d)

Wherein：

X is about 0 to about 0.1；

A includes one or more in Mn or Ti；

Q includes one or more in Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr or Y；

E is 0 to about 0.3；

V is 0 to about 0.5；

W is 0 to about 0.6；

M includes one or more in Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr or Y；

D is 0 to about 0.5；

Y is about 0 to about 1；

Z is about 0.3 to about 1；And

The wherein Li_yMn_2-zM_zO_4-dComponent has spinel structure and the Li_2-wQ_w+vA_1-vO_3-eComponent has layer structure.

27. electrochemical cell as claimed in claim 22, the wherein cathode include active material of cathode, and the cathode activity Material includes：

Li_aA_1-b,R_bD₂,

Wherein：

A be Ni, Co, Mn, or combinations thereof；

R be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, rare earth element, or combinations thereof；

D be O, F, S, P, or combinations thereof；And

0.90≤a≤1.8 and 0≤b≤0.5.

28. electrochemical cell as claimed in claim 22, the wherein cathode include active material of cathode, and the cathode activity Material includes：

Li_aA_1-xR_xDO_4-fZ_f,

Wherein：

A be Fe, Mn, Ni, Co, V, or combinations thereof；

R be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, rare earth element, or combinations thereof；

D be P, S, Si, or combinations thereof；

Z be F, Cl, S, or combinations thereof；

0.8≤a≤2.2；

0≤x≤0.3；And

0≤f≤0.1。

29. a kind of electronic equipment, transporting equipment or telecommunication apparatus, including electrochemical cell according to claim 21.

30. a kind of method, including：

Combination：

A) fluorated solvent；

B) carbonic ester cosolvent；

C) at least one gamma lactone indicated by formula (II)

Wherein

R⁷、R⁸、R⁹And R¹⁰Be each independently H, F, linear chain or branched chain C₁To C₁₀The C of alkyl or linear chain or branched chain₁To C₁₀Fluorine Alkyl；With

D) at least one electrolytic salt；

To form electrolyte composition.